Determining the kinetic rate constants of Fe3O4-to-Fe and FeO-to-Fe reduction by H2

Tang, Qiming; Huang, Kevin

doi:10.1016/j.cej.2022.134771

Title: Determining the kinetic rate constants of Fe₃O₄-to-Fe and FeO-to-Fe reduction by H₂

Journal Article · 19 January 2022 · Chemical Engineering Journal

DOI: https://doi.org/10.1016/j.cej.2022.134771 · OSTI ID:1909396

Tang, Qiming ^[1]; Huang, Kevin ^[2]

Univ. of South Carolina, Columbia, SC (United States); University of South Carolina
Univ. of South Carolina, Columbia, SC (United States)

Steel production using coal accounts for ~ 8% of global carbon emissions. “Green Steel” is a new grand concept proposed recently to make steel from iron ores using renewable derived “Green Hydrogen” to achieve zero carbon emission. The kinetics and rate-limiting steps of iron ore reduction into iron with H₂ as a reducing agent is critically important to the success of this new technology. While reduction of Fe₂O₃ into Fe by H₂ follows multiple steps, the past research on this topic mainly deals with the overall averaged kinetics, giving little information on the elemental and rate-limiting steps. In this work, we report a kinetic study specifically design to attain kinetic rate constants of one-step reduction of Fe₃O₄-to-Fe and FeO-to-Fe. Guided by thermodynamics, we show first how to create in situ the desirable starting oxide phases, i.e., Fe₃O₄ and FeO, with precisely controlled the ratio of partial pressures of H₂O and H₂. We then show time-dependent raw H₂O content data collected by a mass spectrometer and the processed reduction data to extract kinetic rate constants. We found that the kinetics of the two one-step reduction reactions follows nicely the Johnson-Mehl-Avrami (JMA) phase transformation model. The one-step reduction mechanisms and activation energy are also discussed.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Univ. of South Carolina, Columbia, SC (United States)

Sponsoring Organization:: USDOE Office of Fossil Energy (FE); National Science Foundation (NSF)

Grant/Contract Number:: FE0031671

OSTI ID:: 1909396

Journal Information:: Chemical Engineering Journal, Journal Name: Chemical Engineering Journal Vol. 434; ISSN 1385-8947

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (36)

Reduction Kinetics of Metal Oxides by Hydrogen Dang, Jie; Chou, Kuo-Chih; Hu, Xiao-Jun steel research international, Vol. 84, Issue 6 https://doi.org/10.1002/srin.201200242	journal	December 2012
Reduction of Iron Oxides with Hydrogen—A Review Spreitzer, Daniel; Schenk, Johannes steel research international, Vol. 90, Issue 10 https://doi.org/10.1002/srin.201900108	journal	August 2019
The Johnson-Mehl- Avrami-Kohnogorov model: A brief review Fanfoni, M.; Tomellini, M. Il Nuovo Cimento D, Vol. 20, Issue 7-8 https://doi.org/10.1007/BF03185527	journal	July 1998
Reduction kinetics of iron oxide pellets with H2 and CO mixtures Zuo, Hai-bin; Wang, Cong; Dong, Jie-ji International Journal of Minerals, Metallurgy, and Materials, Vol. 22, Issue 7 https://doi.org/10.1007/s12613-015-1123-x	journal	July 2015
Kinetic Studies of Iron Ore–Coal Composite Pellet Reduction by TG–DTA Sah, R.; Dutta, S. K. Transactions of the Indian Institute of Metals, Vol. 64, Issue 6 https://doi.org/10.1007/s12666-011-0065-x	journal	December 2011
Reactions between solids through gaseous intermediates—I reactions controlled by chemical kinetics Sohn, H. Y.; Szekely, J. Chemical Engineering Science, Vol. 28, Issue 10 https://doi.org/10.1016/0009-2509(73)85061-4	journal	October 1973
JMA analysis of the transformation kinetics from the amorphous to the nanocrystalline state Lück, R.; Lu, K.; Frantz, W. Scripta Metallurgica et Materialia, Vol. 28, Issue 9 https://doi.org/10.1016/0956-716X(93)90012-H	journal	May 1993
Crystallization kinetics and the JMAK equation Weinberg, Michael C.; Birnie, Dunbar P.; Shneidman, Vitaly A. Journal of Non-Crystalline Solids, Vol. 219 https://doi.org/10.1016/S0022-3093(97)00261-5	journal	October 1997
Reduction of iron oxides by carbon in a circulating fluidized bed reactor Srinivasan, N. S. Powder Technology, Vol. 124, Issue 1-2 https://doi.org/10.1016/S0032-5910(01)00484-3	journal	April 2002
Influence of microstructure and atomic-scale chemistry on the direct reduction of iron ore with hydrogen at 700°C Kim, Se-Ho; Zhang, Xue; Ma, Yan Acta Materialia, Vol. 212 https://doi.org/10.1016/j.actamat.2021.116933	journal	June 2021
Feasibility study of the use of by-product iron oxide and industrial off-gas for application to chemical looping hydrogen production Cho, Won Chul; Lee, Doyeon; Kim, Chang Hee Applied Energy, Vol. 216 https://doi.org/10.1016/j.apenergy.2018.02.078	journal	April 2018
Topochemical approach of kinetics of the reduction of hematite to wüstite Piotrowski, K.; Mondal, K.; Wiltowski, T. Chemical Engineering Journal, Vol. 131, Issue 1-3 https://doi.org/10.1016/j.cej.2006.12.024	journal	July 2007
Reduction of hematite (Fe2O3) to wüstite (FeO) by carbon monoxide (CO) for chemical looping combustion Monazam, Esmail R.; Breault, Ronald W.; Siriwardane, Ranjani Chemical Engineering Journal, Vol. 242 https://doi.org/10.1016/j.cej.2013.12.040	journal	April 2014
Effect of gas composition on the kinetics of iron oxide reduction in a hydrogen production process Piotrowski, K.; Mondal, K.; Lorethova, H. International Journal of Hydrogen Energy, Vol. 30, Issue 15 https://doi.org/10.1016/j.ijhydene.2004.10.013	journal	December 2005
Steam-iron process: Influence of steam on the kinetics of iron oxide reduction Lorente, Esther; Herguido, Javier; Peña, Jose Angel International Journal of Hydrogen Energy, Vol. 36, Issue 21 https://doi.org/10.1016/j.ijhydene.2011.07.111	journal	October 2011
Solid state reaction kinetics of iron oxide reduction using hydrogen as a reducing agent Barde, Amey A.; Klausner, James F.; Mei, Renwei International Journal of Hydrogen Energy, Vol. 41, Issue 24 https://doi.org/10.1016/j.ijhydene.2015.12.129	journal	June 2016
Utilization and impacts of hydrogen in the ironmaking processes: A review from lab-scale basics to industrial practices Ma, Kaihui; Deng, Junyi; Wang, Gang International Journal of Hydrogen Energy, Vol. 46, Issue 52 https://doi.org/10.1016/j.ijhydene.2021.05.095	journal	July 2021
Reduction of fine iron ore via a two-step fluidized bed direct reduction process Zhang, Tao; Lei, Chao; Zhu, Qingshan Powder Technology, Vol. 254 https://doi.org/10.1016/j.powtec.2014.01.004	journal	March 2014
Reduction kinetics of mechanically activated hematite concentrate with hydrogen gas using nonisothermal methods Pourghahramani, Parviz; Forssberg, Eric Thermochimica Acta, Vol. 454, Issue 2 https://doi.org/10.1016/j.tca.2006.12.023	journal	March 2007
Polycrystalline magnetite (Fe3O4) thin films from FeOx/Fe bilayers grown by pulsed laser depositions Goikhman, A.; Shvets, P.; Koneva, U. Thin Solid Films, Vol. 652 https://doi.org/10.1016/j.tsf.2017.11.008	journal	April 2018
Fe₃O₄/ZrO₂ Composite as a Robust Chemical Looping Oxygen Carrier: A Kinetics Study on the Reduction Process Tang, Qiming; Ma, Yuxi; Huang, Kevin ACS Applied Energy Materials, Vol. 4, Issue 7 https://doi.org/10.1021/acsaem.1c01152	journal	July 2021
An Intermediate-Temperature Solid Oxide Iron–Air Redox Battery Operated on O ^2– -Chemistry and Loaded with Pd-Catalyzed Iron-Based Energy Storage Material Zhang, Cuijuan; Huang, Kevin ACS Energy Letters, Vol. 1, Issue 6 https://doi.org/10.1021/acsenergylett.6b00529	journal	November 2016
A Novel and Green Metallurgical Technique of Highly Efficient Iron Recovery from Refractory Low-Grade Iron Ores Liang, Zhikai; Yi, Lingyun; Huang, Zhucheng ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 22 https://doi.org/10.1021/acssuschemeng.9b05423	journal	October 2019
Vibrational Spectroscopic Characterization of Hematite, Maghemite, and Magnetite Thin Films Produced by Vapor Deposition Jubb, Aaron M.; Allen, Heather C. ACS Applied Materials & Interfaces, Vol. 2, Issue 10 https://doi.org/10.1021/am1004943	journal	September 2010
Hydrogen Production via Chemical Looping Redox Cycles Using Atomic Layer Deposition-Synthesized Iron Oxide and Cobalt Ferrites Scheffe, Jonathan R.; Allendorf, Mark D.; Coker, Eric N. Chemistry of Materials, Vol. 23, Issue 8 https://doi.org/10.1021/cm103622e	journal	April 2011
Kinetics of Hematite to Wüstite by Hydrogen for Chemical Looping Combustion Monazam, Esmail R.; Breault, Ronald W.; Siriwardane, Ranjani Energy & Fuels, Vol. 28, Issue 8 https://doi.org/10.1021/ef501100b	journal	July 2014
Hydrogen Production from the Steam−Iron Process with Direct Reduction of Iron Oxide by Chemical Looping Combustion of Coal Char Yang, Jing-biao; Cai, Ning-sheng; Li, Zhen-shan Energy & Fuels, Vol. 22, Issue 4 https://doi.org/10.1021/ef800014r	journal	July 2008
Kinetics and Mechanism of the β- to α-CuAlCl₄ Phase Transition: A Time-Resolved ⁶³Cu MAS NMR and Powder X-ray Diffraction Study Liu, Haiming; Sullivan, Roger M.; Hanson, Jonathan C. Journal of the American Chemical Society, Vol. 123, Issue 31 https://doi.org/10.1021/ja010688v	journal	July 2001
MOF-derived iron as an active energy storage material for intermediate-temperature solid oxide iron–air redox batteries Zhang, Cuijuan; Huang, Kevin Chemical Communications, Vol. 53, Issue 76 https://doi.org/10.1039/C7CC06131E	journal	January 2017
Proton-mediated energy storage in intermediate-temperature solid-oxide metal–air batteries Xu, Nansheng; Zhang, Cuijuan; Huang, Kevin Journal of Materials Chemistry A, Vol. 6, Issue 42 https://doi.org/10.1039/C8TA08180H	journal	January 2018
A novel intermediate-temperature all ceramic iron–air redox battery: the effect of current density and cycle duration Zhao, Xuan; Li, Xue; Gong, Yunhui RSC Advances, Vol. 4, Issue 43 https://doi.org/10.1039/c4ra02768j	journal	January 2014
Cyclic Durability of a Solid Oxide Fe-Air Redox Battery Operated at 650°C Zhao, Xuan; Gong, Yunhui; Li, Xue Journal of The Electrochemical Society, Vol. 160, Issue 10 https://doi.org/10.1149/2.048310jes	journal	January 2013
In-Situ Kinetic Study of Hydrogen Reduction of Fe₂O₃ for the Production of Fe Nanopowder Jung, Sung-Soo; Lee, Jai-Sung MATERIALS TRANSACTIONS, Vol. 50, Issue 9 https://doi.org/10.2320/matertrans.MRA2008472	journal	January 2009
Redution kinetics of hematite and magnetite pellets containing coal char. Seaton, Carlos E.; Foster, James S.; Velasco, Julio Transactions of the Iron and Steel Institute of Japan, Vol. 23, Issue 6 https://doi.org/10.2355/isijinternational1966.23.490	journal	January 1983
Reduction Kinetics of Hematite Powder in Hydrogen Atmosphere at Moderate Temperatures Chen, Zhiyuan; Dang, Jie; Hu, Xiaojun Metals, Vol. 8, Issue 10 https://doi.org/10.3390/met8100751	journal	September 2018
Degradation of Chlorinated Phenols by Zero Valent Iron and Bimetals of Iron: A Review Gunawardana, Buddhika; Singhal, Naresh; Swedlund, Peter Environmental Engineering Research, Vol. 16, Issue 4 https://doi.org/10.4491/eer.2011.16.4.187	journal	December 2011

Similar Records

Iron Ore Reduction by Hydrogen Using a Laboratory Scale Fluidized Bed Reactor: Kinetic Investigation—Experimental Setup and Method for Determination

Journal Article · 2019 · Metallurgical and Materials Transactions. B, Process Metallurgy and Materials Processing Science · OSTI ID:22933460

Spreitzer, Daniel; Schenk, Johannes

Structure-Controlled Oxygen Concentration in Fe₂O₃ and FeO₂

Journal Article · 2018 · Inorganic Chemistry · OSTI ID:1530397

Zhu, Sheng-cai; Liu, Jin; Hu, Qingyang; +5 more

Kinetics of light-induced first-order phase transformation in molecular solids: Fe(btr){sub 2}(NCS){sub 2}{center_dot}H{sub 2}O

Journal Article · 2006 · Physical Review. B, Condensed Matter and Materials Physics · OSTI ID:20853746

Pillet, S; Legrand, V; Souhassou, M; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Hydrogen
Iron oxide reduction
Kinetics
Modeling
One-step reduction

Title: Determining the kinetic rate constants of Fe3O4-to-Fe and FeO-to-Fe reduction by H2

Citation Formats

References (36)

Similar Records

Related Subjects

Title: Determining the kinetic rate constants of Fe₃O₄-to-Fe and FeO-to-Fe reduction by H₂